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Physical review. E

Generalized Hamiltonian of mean-force approach to open quantum systems coupled to finite baths in thermoequilibrium

Xuerui Du, Jianhui Wang, Yongli Ma

Published Feb 24, 2025• 1 citation
Publisher

Abstract

The prevailing method for addressing strong-coupling thermodynamics typically involves open quantum systems coupled to infinite baths in equilibrium through the Hamiltonian of mean force (HMF). However, its applicability to finite baths remains limited. In this work, we transcend this limit by considering the impacts of system-bath coupling which is not only on the system but also on the finite bath feedback. When the bath and system sizes are comparable, they act as each other's effective 'bath'. We introduce a parameter α within [0,1], where α and 1-α act as weighting factors to distribute the system-bath coupling between the system and the bath. Our approach innovatively incorporates the effect of coupling on the respective effective 'bath' into both the system and bath in the statistical factor form. We generalize the HMF and propose quantum Hamiltonians of mean forces to handle the distributed coupling of the system to finite baths. The additional parameter α is determined by minimizing the joint free energy density and is a new thermodynamic quantity representing the finite bath's influence. Examining the damped quantum harmonic oscillator with a finite bath, we find that α affects both states, leading to a complex phase diagram with unique phenomena at critical temperatures T_{L} and T_{R}, including valleys, peaks, negative values, and discontinuities in entropy and specific heat. Notably, these anomalies disappear when α→1, both at high temperatures and in the thermodynamic limit, indicating the negligible influence of coupling on the bath states and reverting to the HMF. Thus, studying finite-sized baths holds substantial significance in small quantum systems.

DOI
10.1103/physreve.111.024139

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The prevailing method for addressing strong-coupling thermodynamics typically involves open quantum systems coupled to infinite baths in equilibrium through the Hamiltonian of mean force (HMF). However, its applicability to finite baths remains limited. In this work, we transcend this limit by considering the impacts of system-bath coupling which is not only on the system but also on the finite bath feedback. When the bath and system sizes are comparable, they act as each other's effective 'bath'. We introduce a parameter α within [0,1], where α and 1-α act as weighting factors to distribute the system-bath coupling between the system and the bath. Our approach innovatively incorporates the effect of coupling on the respective effective 'bath' into both the system and bath in the statistical factor form. We generalize the HMF and propose quantum Hamiltonians of mean forces to handle the distributed coupling of the system to finite baths. The additional parameter α is determined by minimizing the joint free energy density and is a new thermodynamic quantity representing the finite bath's influence. Examining the damped quantum harmonic oscillator with a finite bath, we find that α affects both states, leading to a complex phase diagram with unique phenomena at critical temperatures T_{L} and T_{R}, including valleys, peaks, negative values, and discontinuities in entropy and specific heat. Notably, these anomalies disappear when α→1, both at high temperatures and in the thermodynamic limit, indicating the negligible influence of coupling on the bath states and reverting to the HMF. Thus, studying finite-sized baths holds substantial significance in small quantum systems.
An open quantum system interacting with a heat bath at a given temperature is expected to reach the mean force Gibbs (MFG) state as a steady state. The MFG state is given by tracing out the bath degrees of freedom from the equilibrium Gibbs state of the total system plus bath. When the interaction between the system and the bath is not negligible, it is different from the usual system Gibbs state obtained from the system Hamiltonian only. Using the path integral method, we present the exact MFG state for a coupled system of quantum harmonic oscillators in contact with multiple thermal baths at the same temperature. We develop a nonperturbative method to calculate the covariances with respect to the MFG state. By comparing them with those obtained from the system Gibbs state, we find that the effect of coupling to the bath decays exponentially as a function of the distance from the system-bath boundary. This is similar to the skin effect found recently for a quantum spin chain interacting with an environment. Using the exact results, we also investigate the ultrastrong coupling limit where the coupling between the system and the bath gets arbitrarily large and makes a connection with the recent result found for a general quantum system.
We have studied the specific heat of the (NS + NB) model for an NS-body harmonic oscillator (HO) system which is strongly coupled to an NB-body HO bath without dissipation. The system specific heat of CS(T) becomes NSkB at T → ∞ and vanishes at T = 0 in accordance with the third law of thermodynamics. The calculated CS(T) at low temperatures is not proportional to NS and shows an anomalous temperature dependence, strongly depending on NS, NB, and the system-bath coupling. In particular at very low (but finite) temperatures, it may become negative for a strong system-bath coupling, which is in contrast with non-negative specific heat of a HO system with NS = 1 reported by Ingold, Hänggi, and Talkner [Phys. Rev. E 79, 061105 (2005)]. Our calculation indicates an importance of taking account of finite NS in studying open quantum systems which may include an arbitrary number of particles in general.
For a small system at a low temperature, thermal fluctuation and quantum effect play important roles in quantum thermodynamics. Starting from micro-canonical ensemble, we generalize the Boltzmann–Gibbs statistical factor from infinite to finite systems, no matter the interactions between particles are considered or not. This generalized factor, similar to Tsallis’s q-form as a power-law distribution, has the restriction of finite energy spectrum and includes the nonextensivities of the small systems. We derive the exact expression for distribution of average particle numbers in the interacting classical and quantum nonextensive systems within a generalized canonical ensemble. This expression in the almost independent or elementary excitation quantum finite systems is similar to the corresponding ones obtained from the conventional grand-canonical ensemble. In the reconstruction for the statistical theory of the small systems, we present the entropy of the equilibrium systems and equation of total thermal energy. When we investigate the thermodynamics for the interacting nonextensive systems, we obtain the system–bath heat exchange and “uncompensated heat” which are in the thermodynamical level and independent on the detail of the system–bath coupling. For ideal finite systems, with different traps and boundary conditions, we calculate some thermodynamic quantities, such as the specific heat, entropy, and equation of state, etc. Particularly at low temperatures for the small systems, we predict some novel behaviors in the quantum thermodynamics, including internal entropy production, heat exchanges between the system and its surroundings and finite-size effects on the free energy.
We consider a quantum system linearly coupled to a reservoir of harmonic oscillators. For finite coupling strengths, the stationary distribution of the damped system deviates from the predictions of standard thermodynamics. With the help of the quantum Hamiltonian of mean force, we quantify this deviation exactly for a harmonic oscillator and provide approximations in the limit of high and low temperatures and weak and strong couplings. Moreover, in the semiclassical regime, we use the quantum Smoluchowski equation to obtain results valid for any potential. We finally give a physical interpretation of the deviation in terms of the initial system-reservoir coupling.
We consider the global thermal state of classical and quantum harmonic oscillators that interact with a reservoir. Ohmic damping of the oscillator can be exactly treated with a 1D scalar field reservoir, whereas general non-Ohmic damping is conveniently treated with a continuum reservoir of harmonic oscillators. Using the diagonalized Hamiltonian of the total system, we calculate a number of thermodynamic quantities for the damped oscillator: the mean force internal energy, mean force free energy, and another internal energy based on the free-oscillator Hamiltonian. The classical mean force energy is equal to that of a free oscillator, for both Ohmic and non-Ohmic damping no matter how strong the coupling to the reservoir. In contrast, the quantum mean force energy depends on the details of the damping and diverges for strictly Ohmic damping. These results give additional insight into the steady-state thermodynamics of open systems with arbitrarily strong coupling to a reservoir, complementing results for energies derived within dynamical approaches (e.g. master equations) in the weak-coupling regime.
We construct a finite bath with variable temperature for quantum thermodynamic simulations in which heat flows between a system S and the bath environment E in time evolution of an initial SE pure state. The bath consists of harmonic oscillators that are not necessarily identical. Baths of various numbers of oscillators are considered; a bath with five oscillators is used in the simulations. The bath has a temperaturelike level distribution. This leads to definition of a system-environment microcanonical temperature T_{SE}(t) which varies with time. The quantum state evolves toward an equilibrium state which is thermal-like, but there is significant deviation from the ordinary energy-temperature relation that holds for an infinite quantum bath, e.g., an infinite system of identical oscillators. There are also deviations from the Einstein quantum heat capacity. The temperature of the finite bath is systematically greater for a given energy than the infinite bath temperature, and asymptotically approaches the latter as the number of oscillators increases. It is suggested that realizations of these finite-size effects may be attained in computational and experimental dynamics of small molecules.